Plastic polymer and process of producing the same



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lloward W. dtarlrtveatllier, ltlevv Castle County,

and .arnold lvl. Collirm, lililmington. hel.. asaignors to E. i. du lient de Nemours di Company lltihnington, hell., a corporation oi helse no planing. application .any sv, ieri, serai inl. nativ ai onine. (ci. atvoel this invention relates to the polymerization. ol halogeii-2butadienesl. More particularly it relates to the polymerization ci. chloro-d-butadiene-1,3 (hereinaiter, tor convenience, also called. chloroprenel'. ,Still more particularly it relates to an improved method tor polymerizing chloro-2butaolienell,3 to n plastic product in the presence or organic moditying agents.

Carothers and Collins in their il. ld. Patent lbbfidz disclose that by polymerizing chloro-Z- butadiene-L3 under various conditions it is posu sible to obtain products having a variety oi degrecs of solubility, plasticity, elasticity and strength. rli'hey state that light and pressure and catalysts such as onygen and perorrides inliuence the polymerization.

Carothers. Collins and Kirby disclose .in their U. C. Patent 1,950,438 that the character oi' the product may be modined by carrying out the polymerization in the presence oi inhibitors Among the inhibitors they investigated vrere various organic sulfur compounds.

U. S. Patent 1,967,860, also issued to Carothers, Collins and Kirby discloses that this poly merization may be carried out in the presence of various solvents.

The emulsiiication oi chloro-2butadienehd and its polymerization in that state to obtain a synthetic laten is disclosed in Collins U. S. latent lt'lol. Ordinarily the product obtained by coagulating this emulsion aiter polymerization to a synthetic laterrfis an elastic., essentially non-plastic.' cured rubber-litre material, but it the chloro-Z-butadiene-Lli contains l% oi iodine it polymerizes to a plastic product. Collins also discloses that the addition oi diluents or solvents before or after emulsiilcation tends to impart a greater degree of softness and plasticity' to the nal product. Dales and Downing, in an application filed August 23, 193i, and given Serial No. 741,044 which application was reilled ll/llarch 2, 1937, as application Serial No. 128,630 and was issued November 28, 1933, as U. S. Patent No. 2,138,226, have described an improved method oi emulsion polymerization involving the use of different emulsifying agents.

Williams, in his U. S. Patent 1,950,436, discloses that plastic polymers may be produced by partially polymerizing chloro-Z-butadiene-LS and then separating the unpolymerized material.w He describes a method which involves partially polymerizing chloro-2-butadiene-L3 without the use of solvents, dispersing media. and the like. This method is hereinafter referred to as massive polymerization. l By suitable compounding and curing, these plastic polymerscan be converted into an extremely tough elastic product resembling vulcanized rubber.

llt is an object of this invention to provide an improved method :tor polymerizing compounds of the general formula in which llt. is halogen and h. is hydrogen or a hydrocarbon radical. il. further object is to prov vide an improved method tor polymerizing halogen-2-butaolienes-l,3. it more speciiic object is to provide a method by which high yields ci plastic polymer may be produced iroin chloro-2-n butadiene-l,3 in a single polymerization. n still iurther object is to produce, in a single polym merization, high yields oi a plastic polymer of chloro-2-butadienel,3 resembling unvulcanized lievea rubber in its physical properties and ca pable of being shaped and cured to iorrn a tough elastic mass closely resembling vulcanized natural rubber. Another object is to provide a procn ess which taires place at a more rapid rate than those previously disclosed for the preparation oi' plastic polymers. Other objects Will appear hereinafter.

The objects are accomplished by polymerizlng compounds ci the general formula oni-:owcl-gcnl X n in which it halogen and it is hydrogen or a hydrocarbon radical, and especially chloro-2- butadienel,3 in non-alkaline emulsion in the presence ci an organic modifying agent, which,` vfor the purpose oi this invention, is defined as polymer is formed. It has been found that 'unlill lill

polymerizable acid-stable organic compounds which are capable of forming an addition product with chloro-2-butadiene-l,3 under condi-` tions of polymerization of ch1oro-2-butadiene-1,3 6 are suitable. By conditions of 'polymerization of chloro-2-butadiene-1,3 is meant just what the expression implies;'i. e., under mild conditions of temperature, pressure, time, etc., such as are hereinafter described for the polymerizations of 10 this invention. The preferred halogen butadiene is chloro-2butadiene1,3 and preferably also the emulsion is substantially acid during polymerization. The preferred dispersing medium is water. l5 'I'his application ls a continuation-in-part of applicants copending application, Serial No. 69,738, filed March 19, 1936. The essential features of this invention are that an organic modifying agent, as described above, for example, an unpolymerizable acidstable organic compound which is capable of adding to chloro-2-butadiene-L3 under mild conditions of reaction to form a definite chemical compound be present during the polymerization of the halogen butadiene, that the polymerization be carried out in emulsion and that the emulsion be acid duringh at least a part of the polymerization. It has been found that compounds included in the class of-organic modi- 80 fying agents belong to widely different organic chemical groups, such as:

1. Unsaturated compounds containing one or more carbonyl groups adjacent to the double. bond. By this expression is meantcompoundscontaining the following nucleus,

'2. Aromatic sulilnic acids.. 3 .Aromatic mercaptans. y 4. Mercapto carboxylic acids. 5. Aliphaticmercaptans.

Many specific examples of suitable modifying agents of this type are given below and, in general,l it may besaid that any particular organic compound issuitable which is capable of combining with chloroprene under mild conditions of reaction, as may be determined by carrying out a simple experiment described below. Thus, it is pointed out that, although many of the known modifying agents maybe classified in the ve chemical groups, it is not 'intended that the invention be limited to these groups but instead that it shall include Within its scope any unpolymerizable acid-stable organic compound Vcapable of reacting with' chloroprene as de- 00 scribed above. Aliphatic mercaptans possess .definite advantages over many other compounds in thebroad class.

It is of course understood that 1f a modifying agent is destroyed by the water or other 05 dispersing medium or by the emulsifying agent or, in fact, if the modifying agent reacts to any substantial extent under the conditions of the polymerization with anything present' except the halogen diene or its polymers, it is unsuitable for use in emulsion polymerization employing such medium or /such agent. Furthermore, if the modifying agents as defined above contain free amino or phenolic groups, their use is not, in general, preferred, for the reason that they tend 'llto retard the polymerization to an undesirable extent. Such compounds are, however, included within the s cope of this invention and may be valuable in special cases.

To determine that a given compound is capable of acting as a modifying agent, by the test 5 mentioned above, it is only necessary to allow it to stand with an equimolecular proportion of chloroprene under ,the conditions hereinafter specified for the polymerization of this invention land then te determine whetneii'an addition prod- 1o uct has resulted, lfor exampleby sparation and analysis of the 'resulting'" Ar'nass. Thus, alpla naphthoquinone which is shown in Example 1 of the table below to be a'modifying agent, and chloroprene, warmed together in the proportion of l5 their molecular weights (158 and 88.5), (give the corresponding monomolecular additionefproduct, chloro-tetra-hydro-anthraquinone. Similarly, the modifying agents. thiophenol and thioglycolic acid, when mixed respectively, with eginmolecular 20 proportions of chloroprene and allowed to stand l will give a considerable yield of raddition product in one day and when allowed to stand for three to eight days at ordinary temperature, are almost quantitativelyconverted into addition products 25 believed to be chloro-butenyl-phenyl-sulflde and chloro-butenyl thioglycolic acid, respectively. In

a like manner, a monomolecular addition product is also obtained when normal amyl mercaptan is used instead of thiophenol or thioglycolic acid.

As stated, the polymerizations of this invention are to be carried out in emulsion. The preferred dispersing medium is water but the invention may be applied 4to dispersions in other media as well. In fact, any medium can be used in which chloro- 2butadiene-1,3 can be emulsifled and which does not prevent its polymerization and which prefer- `ably does not even'inhibit the polymerization. 4Thus, glycerol, ethylene glycol and formamide may be used, provided, of course, that the modio fying agent used does not react with them. Emulsions of this type are broadly disclosed in copending applications of Carothers, Serial No. 738,931, filed August 8, 1934, and Dales 8i Downing, Serial No. 73s,929,n1ed Augusta, 1934.

A third essential feature of this invention is that the emulsion in which the polymerization is carried out be acid during at least the latter part of the polymerization. As mentioned above, it w has already been disclosed (U. s. P. 1.967361) that polymerization in alkaline emulsions in the presence of an inhibitor of polymerization (as de lined in U. S. P. 1,950,438), for` example 1% of iodine as in Example 5 of the first patent, gives u a high yield of a plastic product. These products, however, although resembling unvulcanized natural rubber in a general way, cannot be so readily converted as the product of the present in-Y vention to a form having the high elasticity and w strength of vulcanized natural rubber. Furthermore, the use of an alkaline emulsion was indicated, since the emulsifying agents disclosed, for example sodium oleate, give emulsions of sunlcient stability only when alkaline. 65 It has now been found that, when working in acid emulsions mad by the use of acid-stable. emulsifying agents losed in the present application, a much superior plastic product is obtained, provided that the polymerization iscar- 7o ried out in the presence of a small amountof an acid-stable modifying agent as defined above. Moreover, entirely contrary to expectation it has been found that such of the compounds embraced by the present 'invention as have been disclosed 15 anemia ing the latter part of the polymerization. Methliti dfi

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ods of carrying out the present invention in which the emulsion is neutral or Very slightly alkaline at the start of the polymerization are thus within the scope of this invention. Such methods are operable for the reason that as the polymerization proceeds there is a gradual decrease in the pli-l of the emulsion so that even though the polymeriaation be started in a neutral or slightly alkaline emulsion, a substantial portion of it 'will taire place under acid conditions. It is to be understood, however, that the present invention does not include `within its scope any use of alkalme emulsions other than under the conditions just discussed and that as a matter of fact, neither the use of slightly alkaline nor the use of neutral emulsions as starting materials is a preferred embodiment.

Under preferred conditions the emulsion in which the polymerization takes place will be acid vention has heen foundto be applicable are those" which have the above general formula. The definitely preferred member of this group is chloro-E-butadiene-l which, as has been previously disclosed, possesses the ability topolymerize to a rubber-like material which is similar to natural rubber. Although the other halogen dienes included in the class, which have thus f ar heen tested, do not all possess this property to the same degree as chloroprene, they do, nevertheless, polymerize to more or less rubber-like materials and it has been found that if their polymeriaation is carried-out in the presence of a modifying agent as described above, an improved yield of a more plastic polymer is obtained as contrasted with the product obtained from the same halogen diene in the absence of the modifying agent. Thus, by the present invention an increased yield of more plastic polymer may be obtained from bromo-2-butadiene-l,3 and also from chloro-2-methyl-S-butadiene-1,3 when they are polymerized in the presence of these organic modifying agents by the method set forth above. li/lintures of two or more halogen butadienes may .also be polymerized by the method of this invention.

The organic modifying agent may be brought into contact with the halogen diene in any conveulent manner. The reagent may be dissolved or dispersed in either the halogen diene or in the emulsifying medium prior to emulsication or may be added to the emulsion either during or after the emulsiflcation. The modifying agent itself may be added or a salt may be added which upon lthe addition of acid will generate the modlfying agent. It is also possible to add only a part of the modifying agent at the start of the polybelow.

mei-ization and to add the remainder during its course or, where tvvo different modifying agents are used, one may be added at the start and the other during the course.` of the polymerization.

'llhe varied embodiments of this invention are illustrated in the examples collected in Table l, it should be understood, however, that these examples are intended to be illustrative only and are not intended to limit the scope of the invention. Furthermore, Example 7, in which no modifying agent was used, is introduced for comparison` only and is not an embodiment of the present invention.

ln each example, lOl) parts by Weight of chloroprene, substantially free from acetaldehyde, mono vinyl acetylene, divinyl acetylene, methyl vinyl ketone, and dichloro-l,3-butene-2, `were treated with the proportion of modifying agent given in the table and thoroughly emulsled in d() parts by Weight (unless otherwise specified) of the aqueous solution of emulsifying agent indicated therein. if the emulsifying solution as made up showed an alkaline reaction, it was acidiiied to Congo red by the addition of dilute hydrochloric acid. Emulsification was carried out by repeated passage through a high speed centrifugal pump. The resulting emulsion was allowed to polymeriae yat the temperature given in the table until the density specified in the table Was reached. The approximate time required for this reaction is also given but since it has been found to vary somewhat in individual experiments cary ried out under as nearly identical conditions as chloride slowly with constant agitation until co.

agulation was complete, except in examples Where a substituted ammonium salt Was used as emulsifying agent. ln these. cases, coagulation was brought about by pouring the latex, with stirring, into an equal volume of ethyl alcohol. The dispersing agent and salt were removed from the polymer by Washing the coagulum on corrugated uneven speed rolls with water at 50 C. until foaming had practically ceased. The product was inally dried by milling on a rubber mill with smooth'rolls internally cooled with Water, so that the temperature of the polymer did not exceed about 40 C. The yields of dry polymer in per cent are given inthe table.

, The plasticity numbers of the resulting plastic polymers and the tensile strength of the cured products are given in the table. (Plasticity number as used herein is "the thickness in thousandths of an inch of a sample 2.5 cc. in volume in the form of a cylinder 5%," in diameter which has been heated to 80 C. for- 15 minutes and then kept under a Weight of five kilograms for three minutes at 80 C.). The cured, elastic products were obtained by compounding on a rubber mill, 100 parts by weight of the plastic polymer with ve4 parts titl by weight of zinc oxide, ten parts by weight of magnesium oxide and five parts byxweight of rosin example, beta-naphthoquinone, benzoquinone. etc. in which the carbonyl groups are adjacent TABLE I I Tem rature Final Tensile Exemple Mmm gent'wnt Emllsim 589D" 2&6 and density Y, 1d Plasticity strength, number by Wm based 0MM gewent b Wegh time rs.) ei dilatex e number ibs.

. chloroprene asedon ewster Dulymeution at me C M ft Percent 1.-.-.-" iai-Nephthoquinone,d 0.12% v (see below) g3 g2 B11161188 GB01 'riiiepnenetic A2" 2o 24 92 121 3475 te ii' 2 it 1333 i 32 it lili 0p 6110 it: s it iss u si ci: o reagen b-'rhienephihet 1% o 11 (1) 2s 10 1.0 15 02 49 2100 'rnicciwii D 1"/ 20 4 e 1. 042 91 41 2250 p-Nmethiephenei,1% D 1'?r 25 2 1.031 05 -80 3050 Benzylmereaptmowx.. D 17 110 0.5 1.036 a2 is 1815 Tnieiyeeiieeeid,o.1e% D 1U, 40 2 1.032 15 10 v3100 Emy inieg1yee1ete0.5% E26, (2) 20 1a 1.010 90 52 2125 Thiosalicylicacid,0.5% D 1% 20 18 1.040 96 10i 3400 Emulsifying agent: A is eetyl trimethyl ammonium bromide- B is the sodium salts of alkyl naphthelene sulfonic acids e eleeh'eis; E is die sodium een ef abietene Sinfonie acid parts of this solution used per parts of chloroprene. (2 200 parts of this solution used per 1.00 parts of chloroprene. In addition to the above combinations of modifying and emulsifying agents, satisfactory results have been obtained with the following:

Thiophenol and types `C, D or E. Thioglycolic acid and types C or E.

'I'he chloroprene used in the examples was substantially free from acetaldehyde, monovinylacetylene, divinylacetylene, methyl vinyl ketone and dichloro-L3-butene-2. It vis possible to obtain satisfactory, although somewhat inferior, results by the use of a less pure chloroprene, particularly if the polymerization is interrupted when the yield' is less than with the purer material. Thus, for example, chloroprene containing 0.5% acetaldehyde, 0.3% monovinylacetylene, and 2% dichloro-1,3butene2 may be used. Furthermore, by way of additional example, as much as 2% of monovinylacetylene or acetaldehyde or methyl vinyl ketone may be present when the modifying agent is thioglycolic acidwithout seriously decreasing the quality of the polymer obtained. The amount of divinyl acetylene, however, should, preferably, be 0.1% or less. In fact, it is sometimes observed that small amoun of acetaldekhyde and monovinylacetyleneca an increase in the tensile strength ofthe final product. It

will be understood, therefor-@that this inventionv is not limited to the use of pure chloro-2-butadiene-1,301' other halogen2-butadiene1,3, falthough the use of a substantially pure halogen-2- butadiene-1,3 is preferred. Accordingly the-impurities mentioned above or other corresponding ones should not be present in substantial amounts, if the most desirable results are to be obtained, but it should be recognized that the amounts of the various impurities which may be presen-t The broad class of modifying agents whichV may be used in the processes of this invention has been defined above, and numerous specificmembers of the class have been mentioned in the table of examples. By way of further illustration of the class, it is pointed out that instead of alpha-naphthoquinone, used in Example 1, we may use -other unsaturated carbonyl compounds, for

to lthe double bond. Instead of the benzene sulfinic acid of Example 2, we may use the toluene and higher homologous suliinic acids, the naphthalene sulfinic acids, etc. We have found members of the third and fourth groups of modifying agents (aromatic mercaptans and mercapto oarboxylic acids) particularly useful. .Aromatic mercaptans in wide variety have been found valuable, such as not only thiophenol itself and its homologs such as the thiocresols and its substitution products such as the nitro thiophenols and chloro thiophenols but also the thionaphthols and even compounds in which the mercapto groupl is not directly attached to the aromatic nucleus but is contained in a hydrocarbon side chain, such as benzyl mercaptan as illustrated in the above examples. vParticularlyuseful among the fourth class (mercapto carboxylic acids) is thioglycolic acid (mercapto acetic acid). We may also use thiolactic acid, thiomalic acid.. and aromatic members of this group such as thlosalicylic, or esters of these acids, such as ethyl thioglycolate, as illustrated in part in the above examples.

'Mixtures of two or more organic modifying agents may often be used to advantage as well as mixtures of these lwith inorganic modifying agents, such as sulfur dioxide and hydrogen sulnde, provided of course that the 'modifying Menta selected do not r'eact with each other as, for example, thiophenol and benzoquinonc do..

For some purposes it is desirable` to avoid any offensive odor in the final product and accordingly a preferred sub-class of modifying agents are those of the broad class above defined which do not themselves have a strong odor imder the conditions of the polymerization.V Other preferred classes of modifying agents are the aromatic mercaptans, such as the thiophenols, particularly the nitro thiophenols and the mercapto carboxylic acids, particularly, thioglycolic acid. It has also been found that thioglycolic acid and hydrogen sulfide constitute a preferred combination of modifying agents. Combinations of this ltype in which the thioglycolic acid predominates by weight are particularfy good.

The polymerization in the piesence of two or more modifying agents may be varied in the manner generally described' y(both hereinbefore and hereinafter. The use of suli'ui dioxide as a modifying agent is disclosed in a copending application of Starkweather, Serial No. 69,739. flied .lili

assault' lillarch 19, 1936, which was relled March l, 1949, and given Serial No. 321,667, and such use of hydrogen suliide is disclosed in a copending application of Starkweather and Collins. Serial No. 69,737, filed March 19, 1936, which has now inatured into U. S. Patent No. 2,163,256, issued June 2li, 1939. When either of these modifying agents is a component of the Amixture of modifying agents, it will be obvious that the methods for introducing them which are disclosed in the above identified copending applications may be used. as already indicated. it has also been found when employing more than one modifying agent during the polymerization, that it is possible to add the various modifying agents at 'dii'lerent times, employing different methods of be used are the soluble salts ci the sulphate esters ofiong chain aliphatic alcohols (such as the sodium salt of cetyl or octadecyl sulfate), oi sulfonated unsaturated hydrocarbons (such as the sodium salt of abietene sulfonic acidi and of alkyl naphthalene sulfonic acids. The soluble4 salts particularly the sodium salts of the sulfate esters of straight-chain primary aliphatic alcohols containing irom 12 to 13 carbon atoms also constitute a deiinitely preferred class of emulsifying agents. Mixtures of these estersalts in the proportions in which the acids corresponding to the alcohols occur naturally are frequently used be cause ol" their availability. A preferred emulsilying agent of the sulfate ester type is that obtainable by sulration o1 oleyl acetate followed by neutralization with sodium hydroxide. .another type Emulsifylng agent: C is heptadecyl-di(S'chloroghydroxypropyl)amine;

alcohols; E is the sodium salt of abietene sullonic acid.

ln addition to the above combinations of modllying and emulsifying agents, satisfactory results have been obtained with the following:

'rhicphenol and S02 plus types 0,1) or E. Thiophenol and HzS plus types D or'E.

its is apparent from the above examples this invention is not limited to the use of any particular emulsifying agent. Several different types of emulsifying agents have 4been disclosed above and applied to'this invention and, in general, it may (iii be said that any emulsifying agent or mixture of emulsifying agents may be used which is effec-f tive to produce a physically stable emulsion in an acid medium, such as has been described above as the medium in which polymerization is to be carried out, and which emulsiiyingv agent does not seriously inhibit' the polymerization. For example,

vthose disclosed in' the Dales 8: Downing U. S. Pat-' 4chain aliphatic groupsf are suitable. Others which may be mentioned include cetyl pyridinium bromide, octadecyl betaine, octadecyl dimethyl ammonium bromide and diethylamino ethyl oleyi amide hydrochloride.

Other types oi. emulsifying agents which may D is the sodium salts of the sulfate esters oi cctyl and stearyl vby the addition of sodium chloride or other Wam ter-soluble salt. Dispersions containing the reaction products of long chain primary amines may be coagulated merely by making alkaline to Brilliant Yellow and heating to 60 C. The coagula are then generally washed with Water to remove the salt and dispersing agent, which, if allowed to remain, would in most instances increase `the dimculty of milling and also tend to decrease the quality of the cured polymer.

'I'he amount of such emulsifying agents to be employed will, of course, depend upon the effectiveness of the particular agents. Amounts of vemulsifyins,r agent ranging from 0.2%\to 2% based on the water, are employed in the specific emulsions described above. Greater or less amounts of these or other similar agents may be used. The amount necessary is readily determined by experimental trial in anyv given case. At amount suiiicient to prevent separation of a solid or liquid phase should be present but if desired more can be used. According to preferred procedure amounts of emulsifying agent ranging. from 1% to 2% are used. It has been observed, as ill 18, that increasing t e amount of emulslfying agent, in general, results in increasing the speed of polymerization. The present invention includes Within its scope the use of al1 concentrations and amounts of emulsifying agents which tive stable emulsions (i. e., emulsions in which a. solid'oriiquid phase does not separate out) vof halogen butadiene in the presence of acid trated in Examples 16 and titi and the organic modifying agents dened above. It is also possible to add more emulsifying agent during the course of the polymerization, if desired, either continuously or in vone or more batches. Also, it is often desirable to increase the acidity of the emulsion, containing an organic modifying agent, by vaddition of acid, such as hydrochloric, for example, in such a quantity that the emulsion will turn Congo red paper to a decided blue color.

The proportion of modifying agent may be varied considerably, the precise amount used depending partly upon the type of modifying agent and emulsifying agent, and partly upon the properties desired in the product. In general, increasing the proportion of modifying agent increases the plasticity of the uncured polymer, but may decrease the tensile strength of the cured polymer. Large amounts of modifying agent also tend to decrease the rate of polymerization.

It has also been found that to produce a given effect it may require more or less of one modifying agent than of another. Representative modifying agents have been used in varying proportions in the above examples. From these specific illustrations, bearing in mind the remarks above in regard to the effect of increasing or decreasing the amount of a given modifying agent, it is very easy to determine the amount of any modifyingagent of the class useful in the present invention which is required to obtain a desired result.

It is possible to further vary the manner of applying the invention by varying the concentration of the halogen butadiene in the emulsion. There are, of course, certain limits to the concentration of the halogen butadiene which can be dispersed in a given medium. Within these limits', it has been found, moreover, that small amounts of emulsifying solution give thick emulsions which are diiiicult to maintain at the desired temperature, while large proportions of solutions require inconveniently large reaction vessels and excessive amounts of coagulating agents, although it is possible to use such extreme concentrations. It is to be understood, however, that the invention is not limited 4to the particular concentrations of chloroprene used in the examples. 'I'he preferred range for the concentration of chloroprene in the emulsions is 20 to 50% but as indicated other concentrations are within the scope of the invention.

The emulsion of the halogen butadiene may be prepared in any feasible manner, such as, by passing the halogen butadiene together with the emulsifying liquid through a gear pump or a centrifugal pump or by turbulent flow or by agitating the materials with a paddle or stirrer or by shaking them in a suitable container. It has been found that the best products are obtained tion required to produce similar products will. change somewhat with changes in temperature.

With temperatures below 20 C., however, the polymerization is sometimes inconveniently slow,

kwhile above 50 C. the reaction is usually very rapid, and, therefore, hard 'to control on a large scale. It has been observed, however, that increasing the temperature of polymerization reduces the tendency of both the cured and the uncured polymer to become stiff and hard when kept for long periods at low temperatures. The rate of polymerization is also favorably affected by increasing the pressure (for a method of employing increased pressures, see an article by Starkweather, J. yAm. Chem. Soc. 56, 1870 (1934)), and also by increasing the concentration of the emulsifying agent, as has been pointed out.

The products produced by the process illustrated in the above examples will naturally vary considerably in their characteristics, depending upon the particular conditions employed. The extent of polymerization (proportion of chloro-2- butadiene1,3 consumed) has been found to have a considerable effect upon the properties of the polymer, particularly its plasticity number. The selection of the exact point at which the reaction is stopped depends, however, upon the modifying agent used and the degree of plasticity required for the finished product. In general, and particularly under preferred conditions, it has been found that very good results are obtained if the polymerization is stopped sometime after 75% of polymer has been formed, as estimated as described below.

It has beenlfound that the plasticity number may be accurately controlled by determining the extent of polymerization from time to time and interrupting the polymerization (for example, by

adding phenyl beta naphthylamine), when the.

proportion of-chlorobutadiene polymerized has reached the value, determined by previous experiment, corresponding to the desired plasticity. The extent of the polymerization may be determined in a number of ways. The amount of polymer formed may be determined directly, for example by coagulating and drying a sample of the latex or, conversely, the extent of the polymerization may be determined by measuring the amount of unchanged chlorodiene recovered by any known eilicient method (for example, distillation) from the latex or from the serum obtained by coagulation with alcohol. The density of the latex, which is approximately a linear function of the extent of polymerization, may also be used to follow the reaction. An experienced operator can also roughly estimate the extent of polymerization from the consistency of a coagulated sample. In certain cases, it may be desirable to recover the unchanged chlorobutadiene for reuse. This may be done by methods known to the art, such as removal of the chlorobutadiene by distillation from the latex or from the serum resulting from coagulation or by extraction of the coagulum by solvents such as alcohol, followed in each case by suitable purification.

When the polymerization has progressed to the desired stage an antioxidant such as phenylbeta-naphthylamine may be added as disclosed above. 1% of phenyl-beta-naphthylamine, based on the chlorobutadiene is usually added but greater or somewhat less amounts are effective. Ethyl-beta-naphthylamine and other similar agents may be used in place of phenyl-betanaphthylamine but the latter compound is preferred. It is preferably added in the form of an aqueous emulsion. Frequently it is dissolved in benzene or other suitable solvents before emulsication. The method disclosed in the examples produces very good results, but it will be understood. that it may be added in any other conven.

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aasa'siv lent way, if desired. It may also 'be added after coagulation, although not so conveniently.

llhe polymer may be isolated from the aqueous emulsion by any suitablemethod, for example, as disclosed above, where the substituted arnrnoniurn salts are used as emulsifying agents, by adding ethyl alcohol, as shown in Example 1, and where the other emulsifying agents disclosed are used, by adding solid sodium chloride. The polymer may also be obtained from the latex by spray drying-or by evaporation of thin films.

"Unless the emulsifying agent is completely removed irom the polymer in the coagulation step, it may be desirable to remove substantially all of it before the final milling. This is conveniently accomplished by washing with warm water on corrugated rolls or in an internal mixer, by which methods new surfaces oi the polymer are being continuously exposed to washing medium. To assist the extraction of the emulsifying agent, alcohol, acetone or similar solvent which dissolves emulsifying agent but not the polymer, may be used.

llhe coagulum aiter being washed, if necessary, rnay be dried, for example, in a current of air at elevated temperatures up to about lull C. or at subatrnospherlc pressure or by washing with alcohol or may be milled directly, the mechanically generated heat in the latter case assisting the removal ol the water. The temperature of the polymer being milled, however, preferably will not exceed about 100 C. and is preferably much less. The rolls of the mill should, therelore, be cooled, ior example, with `cold water or reirigerating brine.

Volatile material can be removed to any de` sired extent, by any suitable method, for example, by worlring the coagulated polymer on a rubber mill, substantially all of it being removed by working toa constant Weight. This phase of the process may be practiced in other ways, however. l

llt is possible to continue the polymerization in emulsion after partial polymerization in the massive form either in the presence or absence of modifying agents. y ever, not to allow thepolymerization in the massive state, particularly in the absence of modifying agents, to proceed to a point where substantiall amounts of the elastic polymer are formed, ii maximum yields of plastic polymer are desired. The chloroprene may be dissolved or diluted prior to emulsilcatlon, with suitable solvents, such as those described by Carothers, Collins and Kirby in U. S. Patent No. 1,967,860, or the solvents may be added after emulsication.

The further polymerization in emulsion of the partiallyvpolymerized halogen butadiene or of the diluted halogen butadiene may be modified in the various particulars described above for the undiluted monomer, for example, the modifying agent may be added eitherbefore or after emulsication.

rignas been stated above that it is 'generally desirable to remove substantially all of the emulsify'lng agent before final milling. This statement is subject to exception where an a-mmonium salt is used as the emulsifying agent. lt has been found that the ammonium Vsalts are capable of exerting a stabilizing effect on the plastic polymers. from losing their plasticity. It is, therefore generally desirable to avoid removing these salts from the polymer, in so far as possible during the coagulation, washing, etc., steps.

Care must be taken, how- They tend to prevent them` It has also been found that halogen-2-butadienes-1,3 specifically chloro-2-butadiene-l,3, may be polymerlzed in the presence of other materials, such as nlm-forming materials, for example, `polyrnerizable materials containing two carbon atoms in an `open-chain joined by more than one bond, by the methods described above, to produce similar results. A preferred embodiment involves the use of polymerizable materials of the class described, which are miscible with chloroprene.

The polymerization oi halogen-Z-butadienes- 1,3 and particularly of chloro-2-butadiene-L3 in` the presence of other materials is broadly disclosed by Carothers, Collins, and Kirby in U. S.

Patents NOS. 2,029,410; 2,066,329; 2,066,330;4 and 2,066,331; the rst of which issued February 4, i936, and the latter three on January 5, i937. ln general, the process of the Apresent invention is applicable to the polymerizations described in those applications.

When dichloro-2,3butadiene-1,3 is also present during the polymerization of chloro-Z-butadiene-1,3 according to the present invention especially valuable products are obtained. Polymeriration of chloro-2-butadiene-l,3 in the presence of (heldere-2,3-butadienel,3 is disclosed in detail by Carothers and Berchet in il. S. Patent No. l

l,965,369 issued July 3, lg3d-and as in the case of the Carothers, Collins, and liirby patents cited above the present process is applicable generally to the polymerizations disclosed in this Carothers and Berchet patent.

The lact that this invention is applicable to halogen substituted dienes, other than chloroprene, the preferred halogen diene, has been noted above. This phase of the invention is illustrated by the following examples in which the parts are given by weight. llt should be understood, however, that these examples like those above are not intended to be construedas limiting the scope of the invention.

Example 2d An emulsion was prepared using the same ingredients as in Example 16, above, except that al mixture of '75 parts of chloro-2butadiene-1,3 and 25 parts of chloro-Z-methyl-3-butadiene- 1-3 was used in place of the 100 parts of chloro- 2-butadiene-1,3. The emulsion was polymerlzed as in Example 1,6 until the density was 1.028. The product (61% yield) isolated by the method used in the above examples had a plasticity num'- ber of 90 and upon compounding and curing as in the above examples'was found to have a tensile strength of 1925 pounds per square inch.

Example 21 The procedure of Example 20 was repeated using, however, 100 parts of chloro-Z-methyl-B- butadiene-1,3 in place of the 100 parts of the mixture of chloro-2-butadiene-1,3 and chloro-2- methyl-3butadiene-l,3. The yield was 89%. The product was plastic when warm (plasticity number '72 at 80 C.) but at ordinary temperatures was notas readily milled ,as the mixed polymer of Example 20. Polymerizationln the absence of modifying agents, howeven'an'd without emulsiflcation gave a low yield (22%), while in emulsion Without modifying agent the product was non-plastic. Thus, it will be seen that, although the product formed according to the present invention, from halogen dienes other than chloroprene may differ materially from the polymers similarly formed from chloroprene, the process is, nevertheless, applicable to halogen dienes other than chloroprene.

It is possible to carry out the process of the present invention continuously. Thus, the chloroprene may be continuously emulsiiied by introducing ity together with an emulsifying solution into a suitable emulsiiier as described above, said emulsifler being of suchconstruction that the chloroprene is thoroughly emulsied during its passage therethrough'. The modifying and other agents -can also be added with the chloroprene and emulsifying solution so-that the emulsion ithdrawn from the emulsifler is ready for polyyf'merization. Alternatively, the modifying agent may be added continuously by bringing together A a,stream of the emulsion and a stream compris- .i ao

ing the modifying agent. The various alternative lmethods described above for bringing together the starting materials for the polymerization step are applicable to the continuous formafrom the polymerization lvessel has reached the desired stage of polymerization. Continuous polymerization in the presence of the organic modifying agent is quite conveniently effected when the chloroprene is in an emulsied state, and starting with the chloroprene and other ingredientsrof the emulsion, the plastic polymer mal be produced continuously by continuously emulsifying as described above, and then passing the stream of emulsion so prepared for polymerization into thepolymerization vessel and therethrough', as described above.

Iff desired, an antioxidant, such as phenyl-` beta-naphthylamine, may readily be incorporated continuously into a stream comprising the polymer, for example, the stream issuing from the continuous polymerization vessel, by admitting into the stream' comprising the polymer a stream comprising the antioxidant, the stream of antioxidant being admitted at such a rate that the desired amount of antioxidant is added.

'Ihe products of this invention, particularly.

those obtained from chloroprene, are plastic and readily milled, are soluble in benzene, carbon tetrachloride and similar rubber solvents, and, if they contain suitable antioxidants they retain their plasticity and milling properties on storage at room temperature for some time. They are readily converted by heat especially in the presence of suitable compounding ingredients at 120-160 C., to strong tough highly elastic products resembling natural rubber in all essential points and having the additional advantage of bengmuch more resistant to the action of organic solvents -and chemical reagents generally and of not requiring the use of sulfur and organic accelerators.

Hence, it isV obvious that their properties are much the same as the properties of the polymers of chloroprene described by Williams in his U. S. Patent N o. 1,950,436.l They may therefore be put to the same uses asfhe mentions forliis products uct produced by the process of the present invenas well as to others not mentioned by him specically, although included by his broad description. For example, they may be dissolved in suitable solvents such as benzene, etc. and used as v coating compositions, adhesives for wood, glass, 5 metal, paper, cloth, leather and the like, or for the impregnation of porous materials. These polymers may also be put to the uses described for the polymers of chloro-2butadiene1,3 produced by prior processes in the articles appearing in Ind. Eng. Chem. 25, 1219 (1933), 26 33 (1934); and in Rubber Age for December 10, 1931, at Page 213.

To many people. the odor of all these polymers when cured, with the exception of those in which l5 hydrogen sulfide and the more volatile mercaptans, such as thiophenol and benzyl mercaptan, are used as modifying agents, is less oensive than the odor of vulcanized natural rubber. They have so little odor, in fact, as to be to many 20 people substantially odorless.

'Ihe products containing the organic modifying agent in chemical combination thus diifer chemically from all plastic and readily cured polymers previously described in containing in 25 chemical combination the organic modifying agent used in making them. Thus, in Example 5, analysis of the product showed the presence oi' 1.25% of sulfur, corresponding approximately tol .au of the added tmopnenoi. 8

The effect of the modifying agents upon polymerization is illustrated by comparing Example '7, in which no modifying agent was used, with the others. It will be seen that the modifying agents not only lead to the formation of very much more plastic products but also very greatly increase the tensile strength obtainable on curin g. It has been found that under preferred conditions of polymerization as set forth above. the modifying agents, which are capable of forming a monomolecular addition product vwith chloro- 2-butadiene-1,3 under mild conditions of reaction, are largely consumed. As set forth in the preceding paragraph, a portion at least of the modifying agent consumed has been found to have gone into chemical combination with the polymer. If, however, the polymerization is stopped when the concentration of polymerv formed is low or if the modifying agent or agents is replaced in whole or in part as consumed during the polymerization, then some modifying agent, as such, will remain in admixture with the polymer after the polymerization is stopped. The presence of unconsumed modifying agent in the polymer is not objectionable and may, in fact, in some cases be desirable. For example, it has been found that the laromatic mercaptans described above as modifying agents are also capable of stabilizing the plastic polymer. When present, as such, in the polymer` they tend to prevent it from losing its plasticity.

vAs shown in the examples, the plastic prodtion may be compounded and/or moulded and cured to a great variety of elastic products. A wide variety of compounding ingredients and compositions of chloro-2-butadiene1,3 polymer -have been disclosed in the Duprene Manual published August 1, 1934, by E. I. du Pont de Nemours and Company as well as in U. S. Patent No. 1,950,436 and t Ind. Eng. Chem. articles, cited above. The me ods described therein are applicable to polymers `produced by the t5" radicals, while emulsiiied in the presence of a mercapto carboxylic acid, said process being further characterized in that the hydrogen ion concentration of the emulsion of the compound of the general formula is on the acid side of pH? during the entire period of polymerization.

10. 'Ihe process of claim 9 further characterized in that the compound of the general formula is chloro-2-butadiene-L3 and in that the latter compound is emulsifled in water.

11. A plastic polymer of a compound of the general formula in which X is' halogen and R is a member of the group consisting or hydrogen and hydrocarbon radicals, formed by polymerization while emulsiiied in a liquid, which emulsion is acid during the entire period of polymerization, said plastic polymer being further characterized in that it is capable of being readily cured to a highly elastic product and has, in chemical combination, a small amount of a mercapto carboxylic acid.

12. A plastic polymer of chloro-2-butadiene- 1,3 formed by polymerization while emuisiiied in water, which emulsion is acid during the entire period of polymerization, said plastic polymer being further characterized in that it is capable of being readily cured to a highly elastic product and has, in chemical combination, a small amount of a mercapto carboxylic acid.

13. An elastic polymer obtained by curing a plastic polymer of claim 12.

14. The process which comprises polymerizing a compound of the general formula in which X is halogen and R is a member of the' group consisting of hydrogen and hydrocarbon radicals, while emulsified in the presence of an aromatic mercaptan, said process being'further characterized in that the hydrogen ion concentration of the emulsion of the compound of the general formula is on the acid side of pH'? during the entire period of polymerization.

l5. The process of claim 14' further characterized in that the compound of the general formula is chloro-2-butadiene-l,3 and in that the latter compound is emulsified in water.

16. A plastic polymer oi a compound of the general formula in which X is halogen and R is a member of the group consisting oi hydrogen and hydrocarbon radicals, formed by polymerization while emulsiiied in a liquid, which emulsion is acid during the entire period of polymerization, said plastic polymer being further characterized in that it is capable oi being readily cured to a highly elastic product and has, in chemical combination, a small amount of an aromatic mercaptan.

17. A plastic polymer of chloro-2-butadiene- 1,3 formed by polymerization while emulsiiled in aliphatic mercaptan. said process being further characterized in that the hydrogen ion concentration of the emulsion o1' the compound of the general formula is on the acid side of pH? during the entire period ot polymerization.

20. The process of claim 19 further characterized in that the compound of the general formula is chloro-2-butadiene-L3 and in that the latter compound'is emulsiiled in water.

21. A plastic polymer of a compound of the general formula CH=`2C=CHI in which X is halogen and R is a member 0i the group consisting of hydrogen and hydrocarbon radicals, formed by polymerization while emulsiied in a liquid. which emulsion is acid during the entire period or polymerization, said plastic polymer being further characterized in that it is capable of being readily cured to a highly elastic product and has, in chemical combination, a small amount of an aliphatic mercaptan.

22. A plastic polymer of chloro-2 -butadiene- 1,3 formed by polymerization While emulsifled in water, which' emulsion is acid during the entire period of polymerization, said plastic polymer being further characterized in that it is capable of being readily cured to a highly elastic product and has, in chemical combination, a small amount of an aliphatic mercaptan.

23. An elastic polymer obtained by curing a -plastic polymer of claim 22.

24. The process which comprises polymerizing a compound of the general formula in which X is halogen and R is a member oi' the group consisting or hydrogen and hydrocarbon radicals, while emulsiiled in the presence o! thioglycolic acid and hydrogen sulfide, said process being further characterized in that the hydrogen ion concentration of the emulsion of the compound of the general formula is on the acid side'oi.' pH'I during .the entire period of polymerization.

HOWARD W. STARKWEATHER.

ARNOLD M. COLLINS. 

